CN1444593A - Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization - Google Patents
Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization Download PDFInfo
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- CN1444593A CN1444593A CN01813395A CN01813395A CN1444593A CN 1444593 A CN1444593 A CN 1444593A CN 01813395 A CN01813395 A CN 01813395A CN 01813395 A CN01813395 A CN 01813395A CN 1444593 A CN1444593 A CN 1444593A
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F110/06—Propene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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Abstract
This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. In one embodiment, the metallocenes of the present invention may be represented by the formula: wherein M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, hafnium and titanium, most preferably zirconium; R<7> is wherein R<17> to R<24> are as defined for R<1> and R<2>, or two or more adjacent radicals R<17> to R<24>, including R<20> and R<21>, together with the atoms connecting them form one or more rings; M<2> is carbon, silicon, germanium or tin.
Description
Technical field
The present invention relates to metallocenes composition and they in olefinic polymerization, particularly propylene polymerization is with the purposes in the catalyst system preparation.
Background technology
The purposes of metallocenes composition in olefinic polymerization is known.Comprise replacement, the metallocenes of bridge joint indenyl derivative is that significantly their production has the ability of the isotactic propylene polymers of high degree of isotacticity and narrow molecular weight distributions.Be devoted to obtain the more and more propene polymer of high molecular and fusing point that has of metallocene-produced, kept the active suitable effort of suitable catalyst simultaneously.
Have been found that for this purpose metallocenes is the mode that replaces therein, and the direct relation between the molecular structure of the polymkeric substance that obtains.For what replace, bridge joint indenyl types of metals is luxuriant, is well known that type and the layout of substituting group on indenyl now, and the type that connects the bridge of indenyl, determines the polymkeric substance attribute as molecular weight and fusing point.Lamentedly, although can confirm tendency, this moment can not accurately related concrete replacement or bridge joint mode and concrete polymkeric substance attribute.
For example, U.S. patent No.5,840,644 have described and have comprised indenyl derivative that aryl replaces some metallocenes as part, claim this metallocenes to provide and have high degree of isotacticity, the propene polymer of narrow molecular weight distributions and very high molecular weight.
Equally, U.S. patent No.5,936,053 have described and it is said some Metallocenic compound that is used to produce high-molecular-weight propylene polymer.On each indenyl of Metallocenic compound, these metalloceness contain at the concrete hydrocarbon substituent of 2 positions with at 4 locational unsubstituting aromatic yl substituting groups.
WO98/40419 and WO99/42497 have described and have been used to produce some load catalyst system with dystectic propene polymer.The activator of metallocenes composition and they combines with solid support material usually with acquisition be difficult for the inducing reaction catalyst system of device fouling.Yet, the comparing of obtaining if be known that luxuriant with loaded metal not, the metallocene catalyst system of load tends to cause having more low-melting polymkeric substance.
Many researchs in this field at present have been devoted to use metallocene catalyst system under commercial associated process conditions, to obtain propene polymer, the fusing point of this propene polymer is higher than the known metal ocene catalyst system and approaches, or the same high with the propene polymer that uses conventional Ziegler-Natta catalyst system to obtain, promptly 160 ℃ or higher.The inventor has been found that the Metallocenic compound with this ability.
Summary of the invention
The present invention relates generally to the Metallocenic compound represented by following general formula:
Wherein: M is a periodictable 4,5, or the metal of 6 families, preferred zirconium, hafnium and titanium, most preferably zirconium;
R
1And R
2Identical or different, preferably identical, and be one of following: hydrogen atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, C
1-C
10Alkoxyl group, preferred C
1-C
3Alkoxyl group, C
6-C
10Aryl, preferred C
6-C
8Aryl, C
6-C
10Aryloxy, preferred C
6-C
8Aryloxy, C
2-C
10Thiazolinyl, preferred C
2-C
4Thiazolinyl, C
7-C
40Aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40Arylalkenyl, preferred C
8-C
12Arylalkenyl, or halogen atom, preferred chlorine; Or conjugated diene, it is optionally replaced by one or more alkyl, three (alkyl) silyl or three (alkyl) silyl alkyl, and this diolefine contains 30 atoms that are not counted in hydrogen at the most;
R
5And R
6Identical or different, preferably identical and be one of following: hydrogen atom, halogen atom, preferred fluorine, chlorine or bromine atom, C
1-C
10Alkyl, preferred C
1-C
4Alkyl, they can be halogenated, C
6-C
10Aryl, they can be halogenated, preferred C
6-C
8Aryl, C
2-C
10Thiazolinyl, preferred C
2-C
4Thiazolinyl, C
7-C
40Aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40Arylalkenyl, preferred C
8-C
12Arylalkenyl ,-NR
2 15,-SR
15,-OR
15,-OSiR
3 15Or-PR
2 15Group, wherein R
15Be one of following: halogen atom, preferred chlorine atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, or C
6-C
10Aryl, preferred C
6-C
9Aryl;
R
7Be
Wherein:
R
17-R
24As for R
1And R
2Define or two or more adjacent R
17-R
24, comprise R
20And R
21, form one or more rings with the atom that connects them;
M
2Be carbon, silicon, germanium or tin,
Radicals R
3, R
4And R
10Identical or different and have for R
5And R
6Described implication, or adjacent R on two
10Group is combined together to form ring, preferably comprises the ring of about 4-6 carbon atom.
More specifically, the present invention relates generally to the Metallocenic compound represented by following general formula:
M wherein
1Be selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R
1And R
2Identical or different and be one of following: hydrogen atom, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, C
6-C
10Aryl, C
6-C
10Aryloxy, C
2-C
10Thiazolinyl, C
2-C
40Thiazolinyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Arylalkenyl, OH group or halogen atom, or conjugated diene, this conjugated diene are optionally replaced by one or more alkyl, three (alkyl) silyl or three (alkyl) silyl alkyl, and this diolefine contains 30 atoms that are not counted in hydrogen at the most;
R
3Identical or different, and each be hydrogen atom, halogen atom, can halogenated C
1-C
10Alkyl, can halogenated C
6-C
10Aryl, C
2-C
10Thiazolinyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Arylalkenyl ,-NR '
2,-SR ' ,-OR ' ,-OSiR '
3Or-PR '
2Group, wherein: R ' is halogen atom, C
1-C
10Alkyl or C
6-C
10One of aryl;
R
4-R
7Identical or different, and be hydrogen, as for R
3Define or two or more adjacent R
5-R
7Form one or more rings with the atom that connects them;
R
13Be that following general formula is represented:
Wherein: R
17-R
24As for R
1And R
2Define or two or more adjacent R
17-R
24, comprise R
20And R
21, form one or more rings with the atom that connects them;
M
2Be carbon, silicon, germanium or tin;
R
8, R
9, R
10, R
11And R
12Identical or different and have for R
4-R
7Described implication.
The invention further relates to and comprise one or more above compounds and one or more activators or promotor, the metallocene catalyst system of solid support material optionally, with relate to such metallocene catalyst system in olefinic polymerization, the purposes in the propene polymer polymerization particularly.
Invention is described
In one embodiment, metallocenes of the present invention can be described as two (indenyl) Metallocenic compounds of bridge joint, and wherein the bridge joint between the 1-position of indenyl is the group of following general formula:
R wherein
17-R
24Can be identical or different, and each is hydrogen atom, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, C
6-C
10Aryl, C
6-C
10Aryloxy, C
2-C
10Thiazolinyl, C
2-C
4Thiazolinyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Arylalkenyl, OH group or halogen atom, or two or more adjacent R
17-R
24, comprise R
20And R
21, it forms one or more and phenyl condensed ring with phenyl between two parties (intervening) atom; And M
2Be carbon, silicon, germanium or tin and optionally on the rest position of indenyl rings, replace.
In one embodiment, metallocenes of the present invention can be represented by following general formula:
Wherein: M is a periodictable 4,5, or the metal of 6 families, preferred zirconium, hafnium and titanium, most preferably zirconium;
R
1And R
2Identical or different, preferably identical, and be one of following: hydrogen atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, C
1-C
10Alkoxyl group, preferred C
1-C
3Alkoxyl group, C
6-C
10Aryl, preferred C
6-C
8Aryl, C
6-C
10Aryloxy, preferred C
6-C
8Aryloxy, C
2-C
10Thiazolinyl, preferred C
2-C
4Thiazolinyl, C
7-C
40Aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40Arylalkenyl, preferred C
8-C
12Arylalkenyl, or halogen atom, preferred chlorine; R
1And R
2Also can be combined together to form alkane two bases or conjugation C
4-40The diolefine part, it is coordinated to M in metal ring amylene mode
1On; R
1And R
2It also can be identical or different conjugated diene, it is optionally by one or more alkyl, three (alkyl) silyls or three (alkyl) silyl alkyl replace, this diolefine contains 30 atoms being not counted in hydrogen at the most and forms the π title complex with M, and example includes, but are not limited to: 1,4-phenylbenzene-1, the 3-divinyl, 1,3-pentadiene, the 2-methyl isophthalic acid, the 3-pentadiene, 2, the 4-hexadiene, 1-phenyl-1, the 3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1,4-xylyl-1, the 3-divinyl, 1, two (the trimethyl silyl)-1,3-butadienes of 4-, with 1,4-dinaphthyl-1,3-butadiene.
R
5And R
6Identical or different, preferably identical, and be one of following: hydrogen atom, halogen atom, preferred fluorine, chlorine or bromine atom, C
1-C
10Alkyl, preferred C
1-C
4Alkyl, they can be halogenated, C
6-C
10Aryl, they can be halogenated, preferred C
6-C
8Aryl, C
2-C
10Thiazolinyl, preferred C
2-C
4Thiazolinyl, C
7-C
40Aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40Arylalkenyl, preferred C
8-C
12Arylalkenyl ,-NR
2 15,-SR
15,-OR
15,-OSiR
3 15Or-PR
2 15Group, wherein R
15Be one of following: halogen atom, preferred chlorine atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, or C
6-C
10Aryl, preferred C
6-C
9Aryl;
R
7Be
Wherein:
R
17-R
24As for R
1And R
2Define or two or more adjacent R
17-R
24, comprise R
20And R
21, form one or more rings with the atom that connects them;
M
2Be carbon, silicon, germanium or tin and
Radicals R
3, R
4And R
10Identical or different and have for R
5And R
6Described implication, or adjacent R on two
10Group is combined together to form ring, preferably comprises the ring of about 4-6 carbon atom.
Special preferred metallocenes of the present invention is represented by following general formula:
M wherein
1Be selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferred zirconium, hafnium or titanium, most preferably zirconium;
R
1And R
2Identical or different, and be one of following: hydrogen atom, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, C
6-C
10Aryl, C
6-C
10Aryloxy, C
2-C
10Thiazolinyl, C
2-C
40Thiazolinyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Arylalkenyl, OH group or halogen atom, or conjugated diene, this conjugated diene are optionally replaced by one or more alkyl, three (alkyl) silyl or three (alkyl) silyl alkyl, and this diolefine contains 30 atoms that are not counted in hydrogen at the most;
Preferred R
1And R
2Identical and be C
1-C
3Alkyl or alkoxyl group, C
6-C
8Aryl or aryloxy, C
2-C
4Thiazolinyl, C
7-C
10Aralkyl, C
7-C
12Alkaryl or halogen atom, preferred chlorine;
R
3Identical or different, and each be hydrogen atom, halogen atom, can halogenated C
1-C
10Alkyl, can halogenated C
6-C
10Aryl, C
2-C
10Thiazolinyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Arylalkenyl ,-NR '
2,-SR ' ,-OR ' ,-OSiR '
3Or-PR '
2Group, wherein: R ' is halogen atom, C
1-C
10Alkyl, C
6-C
10One of aryl; Preferred R
3It or not hydrogen atom;
Preferred each R
3Identical and be fluorine, chlorine or bromine atom, can halogenated C
1-C
4Alkyl, can halogenated C
6-C
8Aryl ,-NR '
2,-SR ' ,-OR ' ,-OSiR '
3Or-PR '
2Group, wherein: R ' is chlorine atom, C
1-C
4Alkyl, C
6-C
8One of aryl;
R
4-R
7Identical or different, and be hydrogen, as for R
3Define or two or more adjacent R
5-R
7Form one or more rings with the atom that connects them;
R
13Be that following general formula is represented:
Wherein: R
17-R
24As for R
1And R
2Define or two or more adjacent R
17-R
24, comprise R
20And R
21, form one or more rings with the atom that connects them; Preferably, R
17-R
24Be hydrogen.
M
2Be carbon, silicon, germanium or tin, preferred silicon; With
R
8, R
9, R
10, R
11And R
12Identical or different and each have for R
4-R
7Described implication.
Independent as used herein or bonded term " alkyl " expression can optionally replace straight chain, side chain or cyclic alkyl.The example of group comprises like this, but be not limited to, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, hexyl, octyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group etc. comprise their replacement analogue.Term " thiazolinyl " expression contains straight chain, side chain or the cyclic hydrocarbon group of one or more pairs of keys.These thiazolinyls can optionally replace.The example of suitable thiazolinyl includes, but not limited to vinyl, propenyl, allyl group, 1, and 4-butadienyl, cyclopropenyl radical, cyclobutene base, cyclopentenyl, cyclohexenyl, cyclooctene base etc. comprise their replacement analogue.Term " alkoxyl group " expression alkyl ether groups, wherein: the term alkyl as defined above.The example of suitable alkyl ether groups includes, but not limited to methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy etc.Term " aryl " expression phenyl, Azulene base or naphthyl etc., they can optionally comprise heteroatoms and/or have one or more substituting groups, for example alkyl, alkoxyl group, halogen, hydroxyl, amino, nitro etc.
Following is particularly preferred metallocenes:
Dichloro rac-9-silicon fluorenes two bases (silafluorendiyl) (2-methyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-ethyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-n-propyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-sec.-propyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-normal-butyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-isobutyl--4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-sec-butyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl-4-phenyl indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (2-methyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-ethyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-n-propyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-sec.-propyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-normal-butyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-isobutyl--4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (2-sec-butyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-methyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-ethyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-n-propyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-sec.-propyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-normal-butyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-isobutyl--4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-sec-butyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl-4-phenyl indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (2-methyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-ethyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-n-propyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-sec.-propyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-normal-butyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-isobutyl--4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (2-sec-butyl-4-phenyl indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl-4-phenyl indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two--trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dichloro rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dichloro rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close zirconium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Dimethyl rac-9-silicon fluorenes two bases (the 2-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Close hafnium;
Rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Hafnium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl)
2Hafnium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-methyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-ethyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-n-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec.-propyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-normal-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-isobutyl-, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-sec-butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
Rac-9-silicon fluorenes two bases (the 2-tertiary butyl, 4-[3 ', 5 '-the phenylbenzene phenyl] indenyl)
2Zirconium η
4-1,4-phenylbenzene-1,3-butadiene;
The substituting group that " 9-silicon fluorenes two bases " are expressed as follows:
According to from document, U.S. patent Nos.5 for example, the known current techique of 789,634 and 5,840,644 (two documents are incorporated herein by reference in full at this) prepares metallocenes of the present invention.
Generally speaking, the metallocenes of this type is by following synthetic: (R wherein
4=H) (a) be in ethers type solvent, at room temperature by NiCl
2(PPh
3)
2Aryl coupled reaction between catalytic 4-halogen replacement indenes and the aryl grignard reagent is to reflux.Usually by column chromatography or distillation refined products.(b) be by alkyl anionic metal salt (as n-BuLi) take off proton to form the indenes thing, subsequently by with reaction as the suitable bridge joint precursor stipulated among the embodiment.Reaction is carried out in ethers type solvent usually at ambient temperature.By column chromatography or the refining final product of distillation.(c) be to take off proton to form two negatively charged ion by the two of alkyl negatively charged ion (as n-BuLi), subsequently with metal halide (as ZrCl
4) reaction.Reaction is carried out in ethers type or aromatic solvent usually at ambient temperature.Obtain final product by thick solid recrystallization.
Metallocenes of the present invention is the high activity catalyst component of olefinic polymerization.Metallocenes preferably adopts with the chiral racemic body.Yet, also can use pure enantiomorph with (+) or (-) form.Pure enantiomorph allows the preparation optical active polymer.Yet, the meso-form that should remove metallocenes, this be since mirror symmetry at the central metal atom place the polymerization activity center (atoms metal) in these compounds of making no longer be chirality and therefore can not produce highly isotactic polymkeric substance.If do not remove meso-form, except that isotactic polymer, form nonstereospecific polymer.Use for some, this may be fully required.
When comprising the metallocenes of some bridge joint group, preparation carries out racemize/meso metallocenes isomer separation.We have found that when the bridge joint group R
13, when being represented by following general formula, this is true:
Wherein: M
2And R
17-R
24As defined above.
Metallocenes is general to be used in combination with the activator of some forms to produce active catalyst system.Term " activator " and " promotor " exchange use and are defined herein as any compound or the component that expression can strengthen one or more metallocenes abilities that are used for olefin polymerization, or the binding substances of compound or component.Alkylaluminoxane is used as the metallocenes activator usually as methylaluminoxane (MAO).Alkylaluminoxane generally comprises 5-40 repeating unit:
The R (AlRO) of linear kind
xAlR
2With
(AlRO) of ring-type kind
x
Wherein R is the C that comprises mixed alkyl
1-C
8Alkyl.Especially preferably wherein R is the compound of methyl.Can sentence solution from commercial retailer and obtain aluminoxanes solution, particularly methylaluminoxane solution with various concentration.The various methods that prepare aikyiaiurnirsoxan beta are arranged, and their non-limitative example is described in the following document: U.S. patent Nos.4,665,208,4,952,540,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235,081,5,103,031 and EP-A-0 561476, EP-B1-00 279 586, EP-A-0594-218 and WO94/10180, each document is incorporated herein by reference in full at this.
It is luxuriant that the ionization activator also can be used for activated metal.These activators are neutral or ionic, or as the compound of four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, its ionization neutral metal cyclopentadinyl compound.Such ionization compound can comprise active proton, or associates with the residual ion of ionization compound, but not coordination or only loose some other positively charged ions that are coordinated on the ionization compound residual ion.Also can use the binding substances of activator, for example, aikyiaiurnirsoxan beta and ionization activator binding substances, referring to for example, WO94/07928.
Be used for polycoordination is appeared at following document by the description of the ionic catalyst of non-coordination anion activatory metallocenes cation composition work early: EP-A-0 227 003, EP-A-0277 004 and U.S. patent No.5,198,401 and WO-A-92/00333 (each document is hereby incorporated by).These teach literatures required preparation method, wherein: by the negatively charged ion precursor with metallocenes protonated make from transition metal capture the alkyl/hydride group so that it for following both: cationic and by non-coordination anion charge balance.Suitable ion salt comprises quaternary borate or contains the fluoro aryl substituting group such as the aluminium salt of phenyl, xenyl or naphthyl.
Term " non-coordination anion " (NCA) is represented such negatively charged ion, and it is not coordinated on this positively charged ion or therefore it be coordinated on this positively charged ion that remainder enough is easy to be replaced by neutral Lewis base a little less than only." compatible " non-coordination anion be when the initial title complex that forms decomposes, be not degraded to neutral those.In addition, negatively charged ion can not shift anion substituent or fragment and form neutral four-coordination Metallocenic compound and neutral by product to cause it from negatively charged ion to positively charged ion.Being used for non-coordination anion of the present invention is those materials, and they are compatible, and the luxuriant positively charged ion of stable metal under+1 time its ionic charge situation of balance still keeps allowing enough volatilities of being replaced by olefinic or acetylene series unsaturated monomer between polymerization period.
The purposes that does not comprise active proton but can produce the ionization ionic compound of luxuriant positively charged ion of reactive metal and non-coordination anion also is known.Referring to, for example, EP-A-0 426 637 and EP-A-0 573 403 (each document is hereby incorporated by).The other method of preparation ionic catalyst is used ionization negatively charged ion precursor, and it initially is neutral lewis acid but forms positively charged ion and negatively charged ion, for example use of three (pentafluorophenyl group) borine with the ion reaction of Metallocenic compound the time.Referring to EP-A-0 520 732 (being hereby incorporated by).Negatively charged ion precursor that also can be by comprising burning group and anionic group prepares the addition polymerization ionic catalyst by the oxidation of transistion metal compound metal center, referring to EP-A-0 495 375 (being hereby incorporated by).
When metal ligand (for example comprises the halogen part, the bicyclic pentadiene zirconium dichloride) time, it can not carry out ionization and capture under standard conditions, they can by with organometallic compound such as lithium hydride or aluminum hydride or alkyl, the known alkylated reaction of alkylaluminoxane, Grignard reagent etc. and transforming.In-situ method referring to EP-A-0 500 944 and EP-A1-0 570 982 (each document is hereby incorporated by), this method had been described before the activated anionic compound adds or with the adding of activated anionic compound, the reaction of alkylaluminium cpd and two halogen substituted metal cyclopentadinyl compounds.
The carrying method that comprises the ionic catalyst of metallocenes positively charged ion and NCA is described in the following document: WO9950311, U.S. patent Nos.5,643,847 and 5, the U.S. patent application No.09184389 (each document is hereby incorporated by) that the U.S. patent application No.09184358 that on November 2nd, 972,823,1998 submitted to and on November 2nd, 1998 submit to.
When the activator of the catalyst composition of metallocenes load is NCA, preferably at first in carrier compositions, adds NCA and add metalloscene catalyst subsequently.When activator is MAO, preferably MAO and metalloscene catalyst are dissolved in the solution together.Then carrier is contacted with MAO/ metallocene catalyst agent solution.Other method and addition sequence are obvious for those skilled in the art.
The load of preferred use small porous particle material (for example, talcum, inorganic oxide, butter such as magnesium chloride and resinous material such as polyolefine or polymer complex) is used to prepare the catalyst system of the present composition.
Preferably, solid support material is the porous inorganic oxide material, and it comprises from the periodic table of elements 2,3, those of 4,5,13 or 14 family's metal/quasi-metal oxides.Especially preferably silicon-dioxide, aluminum oxide, silica-alumina, and composition thereof.Can separately or combine other inorganic oxide that adopts with silicon-dioxide, aluminum oxide or silica-alumina is magnesium oxide, titanium oxide, zirconium white etc.
Preferred carrier materials is that surface-area is 10-700m
2/ g, total pore volume are that 0.1-4.0cc/g and mean pore size are the porous silica of 10-500 μ m.More preferably, surface-area is 50-500m
2/ g, pore volume are that 0.5-3.5cc/g and mean pore size are 20-200 μ m.The most required surface-area is 100-400m
2/ g, pore volume are that 0.8-3.0cc/g and mean pore size are 30-100 μ m.The mean pore size of typical case's porous carrier materials is the 10-1000 dust.The average pore diameter of the solid support material that preferably, uses is as the 50-500 dust and the most required be the 75-350 dust.Can need under 100 ℃-800 ℃, silicon-dioxide be dewatered 3-24 hour anywhere especially.
Can adopt many mode bond luxuriant, activator and solid support material.Also can use more than a kind of metallocenes.The example of suitable carrier technology is described in U.S. patent Nos.4,808,561 and 4,701,432 (each document is hereby incorporated by).Preferably with metallocenes and activator in conjunction with and their reaction product loaded on the porous carrier materials, as described at following document: U.S. patent No.5,240,894 and WO94/28034, WO96/00243 and WO96/00245 (each document is hereby incorporated by).Perhaps, can separately metallocenes be activated in advance and combine with solid support material separately or together then.If separately loaded metal is luxuriant, then preferred, before being used for polymerization, with their dryings then with the powder combination.
No matter whether with metallocenes with their activator contacts separately in advance or deny with metallocenes and activator combination immediately, can preferably be applied to reaction soln cumulative volume on the porous support in some cases less than 4 times of porous support total pore volumes, be more preferably less than 3 times of porous support total pore volumes and even more preferably greater than 1-less than 2.5 times of porous support total pore volumes.The program of measuring the porous support total pore volume is being known in the art.A kind of such method is described in volume 1, the test method in the catalyst research, Academic Press, 1968,67-96 page or leaf.
The catalyst system of load can be directly used in polymerization maybe can use method pre-polymerized catalyst system well known in the art.For prepolymerized details, referring to United States Patent(USP) Nos. 4,923,833 and 4,921,825 and EP0 279 863 and EP0 354 893 (each document is incorporated herein by reference in full at this).
Metallocene catalyst system described here is used for the polymerization of all types alkene.This comprises the production homopolymer, multipolymer, the polymerization process of terpolymer etc. and segmented copolymer and impact-resistant copolymerized thing.Can be in solution, in suspension or in gas phase, continuously or off and on, or its any combination, in one or more steps,, more preferably 30 ℃-80 ℃, carry out these polymerization processs under preferred especially 50 ℃-80 ℃ temperature preferably at 60 ℃-200 ℃.Use general formula R
aCH=CH-R
bAlkene carry out polymerization or copolymerization.In this general formula, R
aAnd R
bIdentical or different and be hydrogen atom or the alkyl that contains 1-14 carbon atom.Yet, R
aAnd R
bPerhaps can form ring with the carbon atom that connects them.The example of alkene is ethene, propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornylene and norbornadiene like this.Especially, polypropylene and ethene.Metallocenes of the present invention and metallocene catalyst system are suitable for the polymerization of acronal most.
As needs, add hydrogen as molecular weight regulator and/or to increase activity.The total pressure of polymerization system is the 0.5-100 crust.Preferably in the industry pressure range interested especially of 5-64 crust, carry out polymerization.
Typically, in polymerization, use metallocenes: every dm with following concentration based on transition metal
3Solvent or every dm
3Reactor volume 10
-3-10
-8Mol, preferred 10
-4-10
-7The mol transition metal.When aikyiaiurnirsoxan beta was used as promotor, its working concentration was every dm
3Solvent or every dm
3Reactor volume 10
-5-10
-1Mol, preferred 10
-4-10
-2Mol.Use other promotor of mentioning with suitable equimolar amount about metallocenes.Yet in principle, higher concentration also is possible.
If polymerization is carried out be suspending or solution polymerization, typically use be generally used for the Ziegler low pressure process inert solvent for example, in aliphatic series or clicyclic hydrocarbon, carry out polymerization; Its example is propane, butane, hexane, heptane, octane-iso, hexanaphthene and methylcyclohexane.Also can use benzene or hydrogenated diesel cut.Also can use toluene.Preferably in liquid monomer, carry out polymerization.If the use inert solvent is with gas or liquid form metering monomer.
At catalyzer, before particularly supported catalyst adds, can be with another kind of alkylaluminium cpd, for example, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum or prenyl aluminium are introduced in the reactor in addition so that polymerization system is inert (for example being used for the catalyzer poison that alkene exists).Concentration with the Al of every kg reactor content 100-0.01mmol adds this compound in polymerization system.Preferably concentration is triisobutyl aluminium and the triethyl aluminum of the Al of every kg reactor content 10-0.1mmol.This allows in load catalyst system synthetic at the low-level Al/M that selects down
1Mol ratio.
Yet in principle, the use that is used for the catalytic other material of polyreaction is not necessary, that is, system according to the present invention can be used as unique catalyzer of olefinic polymerization.
The method according to this invention significantly is the following fact: the metallocenes of description can obtain having very high molecular weight, fusing point, very the propene polymer of high tacticity has high catalyst activity in 50 ℃-80 ℃ industry polymerization temperature scope interested especially.
Even in temperature, when being used for method under the commercial correlated condition of pressure and catalyst activity, catalyst system of the present invention can provide the polymkeric substance of special high molecular and fusing point, particularly alfon and multipolymer.Preferred fusing point is at least 155 ℃ high, and more preferably at least 157 ℃, even more preferably at least 157 ℃ and most preferably 160 ℃ or bigger.
Catalyst system of the present invention also can provide the propene polymer with high stereotaxis degree and regional degree of orientation.Under greater than 98% triad tacticity, isotactic propylene polymers prepared according to the methods of the invention can have the ratio of inserting propylene units less than 0.5% 2-1-.Preferably there is not measurable 2-1-to insert the propylene units ratio.Use
13C-NMR is according to J.C.Randall, and polymer sequence is measured: carbon-13NMR method, the triad tacticity is measured in Academic Press New York 1978.The polymkeric substance that uses method described here preparation has found purposes in all that comprise fiber, articles injection-moulded, film, pipe etc. are used.
Although by describing and illustrated the present invention with reference to specific embodiment, what can be appreciated by those skilled in the art is to the invention provides it and self do not change in many differences of this explanation.Then, only should be used for determining the purpose of true scope of the present invention with reference to appended claim owing to these reasons.
Although have single dependency according to U.S. patent practice dependent claims, each feature in any dependent claims can combine with each feature in other dependent claims or the main claim.
Embodiment
In the loft drier of nitrogen purge, carry out the test of all air-sensitive.All solvents are available from commercial source.4-bromo-2-methyl indenes, 4-chloro-2-methyl indenes and three (pentafluorophenyl group) borine in toluene are available from commercial source.Aluminum alkyls with hydrocarbon solution available from commercial source.Commercial methylaluminoxane (" MAO ") with the 30wt% solution in toluene available from Albemarle.Obtain metallocenes dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl) from commercial source
2Close zirconium and dichloro-dimethyl silicon two bases (4-[1-naphthyl]-2-methyl indenyl)
2Close zirconium.
Comparative Examples 1
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl)
2Close zirconium
Load contrast metallocene catalyst system 1
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl)
2Close zirconium/MAO
In the 100mL round-bottomed flask, with dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl) 2 close zirconium (contrast metallocenes 1,0.055g) join MAO solution (6.74g, 7.2mL) in and stirred 20 minutes.This material is filtered and adopts toluene (14mL) washing by medium frit funnel.In bonded filtrate, add dehydrated silica (4.0g, Davison 948Regular, 600 ℃ of dehydrations).This slurry was stirred 20 minutes, then under 40 ℃ under vacuum on rotatory evaporator dry 2 minutes up to liquid evaporation with amount to about 2 hours 22 minutes with solid is further dry then.The catalyst recovery of load is greenish orange look, free-flowing solid (5.63g).
Comparative Examples 2
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-[1-naphthyl] indenyl)
2Close zirconium
Load contrast metallocene catalyst system 2
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-[1-naphthyl] indenyl)
2Close zirconium/MAO
In the 100mL round-bottomed flask, with dichloro racemize dimethyl-silicon two bases (2-methyl-4-[1-naphthyl] indenyl)
2Close zirconium (contrast metallocenes 2,0.064g) join MAO solution (6.74g, 7.2mL) in and stirred 20 minutes.This material is filtered and adopts toluene (14mL) washing by medium frit funnel.In bonded filtrate, add dehydrated silica (4.0g, Davison 948 Regular, 600 ℃ of dehydrations).This slurry was stirred 20 minutes, then under 40 ℃ under vacuum on rotatory evaporator dry 2 minutes up to liquid evaporation with amount to about 2 hours with solid is further dry then.The catalyst recovery of load is orange, free-flowing solid (4.72g).
Embodiment 3
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)
-2-methyl indenes)] close zirconium
4-[3 ', 5 '-di-tert-butyl-phenyl]-2-methyl indenes
With 4-chloro-2-methyl indenes (6.1g, 37mmol) and NiCl
2(PPh
3)
2(1.8g 2.8mmol) is dissolved in the Et of 150mL
2Among the O.To be Et
23 of O solution, (10g 37mmol) joins in the solution and at room temperature will react to stir and spend the night 5-di-tert-butyl-phenyl magnesium bromide.After stirred overnight, will react and adopt H
2The slow quenching of O is with the unreacted Grignard reagent that neutralizes.Adopt the 10%HCl (aq) of 100mL to handle subsequently solution, adopt the saturated sodium bicarbonate aqueous solution neutralization.Organic layer adopted dried over mgso and remove and desolvate by rotary evaporation.Be loaded into remaining resistates on the silicagel column and employing hexane wash-out.Output is 4.6g (40%).
Lithium 4-[3 ', 5 '-di-tert-butyl-phenyl]-2-methyl indenes
With 4-[3 ', 5 '-di-tert-butyl-phenyl]-(4.7g 15mmol) is dissolved in the 80mL pentane 2-methyl indenes.In this solution, add the n-BuLi (2.5M in hexane) of 5.9mL and allow reaction at room temperature to stir 4 hours.White solid precipitates from solution and this solid is filtered collection by frit and adopts other pentane washing.Output is 3.6g (78%).
Two (the 4-(3 ', 5 ' di-tert-butyl-phenyl)-2-methyl indenes of 9-silicon fluorenes
With 9, (1.2g 9.2mmol) is dissolved among the THF of 80mL 9-two chloro-9-silicon fluorenes.In this solution, slowly be incorporated as the lithium 4-[3 ' of dried powder, 5 '-di-tert-butyl-phenyl]-(3.0g's 2-methyl indenes 9.2mmol) and with solution stirring spends the night.After at this moment, in a vacuum except that desolvating and resistates being dissolved in ether.Solution is filtered to remove LiCl and to remove the crude product (4.1g) that desolvates and be used as next step in a vacuum by frit.
[9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-methyl indenes)] ZrCl
2
Will (4.1g 5.5mmol) dissolves in the 50mL ether from the thick solid of previous steps.In this solution, slowly add n-BuLi (4.4mL, the 2.5M in hexane) and at room temperature stirred 3 hours.Solution is cooled to-30 ℃ and will be the ZrCl of dried powder
4(1.28g, 4.6mmol) adding was also at room temperature stirred 2 hours.Solvent is removed under vacuum and toluene is joined in the thick resistates.Solution filtered to remove LiCl filtrate is concentrated and under heating, add pentane.Solution is cooled off with induced crystallization.The output of pure racemic isomer is 187mg (3.7%).
Loaded metal ocene catalyst system 3
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)
-2-methyl indenes)] close zirconium
In the 100mL round-bottomed flask, with the dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-methyl indenes)] close zirconium (0.085g) join MAO solution (6.74g, 7.2mL) in and stirred 20 minutes.This material is filtered and adopts toluene (14mL) washing by medium frit funnel.In bonded filtrate, add dehydrated silica (4.0g, Davison 948Regular, 600 ℃ of dehydrations).This slurry was stirred 20 minutes, then under 40 ℃ under vacuum on rotatory evaporator dry 2 minutes up to liquid evaporation, and amount to about 2 hours 20 minutes with solid is further dry then.The catalyst recovery of load is rose pink, free-flowing solid (5.24g).
Embodiment 4
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)
-2-sec.-propyl indenes)] close zirconium
4-[3 ', 5 '-di-tert-butyl-phenyl]-2-sec.-propyl indenes
With 4-chloro-2-sec.-propyl indenes (7.2g, 37mmol) and NiCl
2(PPh
3)
2(1.8g 2.8mmol) is dissolved in the Et of 150mL
2Among the O.To be Et
23 of O solution, (10g 37mmol) joins in the solution and at room temperature will react stirring and spend the night 5-di-tert-butyl-phenyl magnesium bromide.After stirred overnight, will react and adopt H
2The slow quenching of O is with the unreacted Grignard reagent that neutralizes.Adopt the 10%HCl (aq) of 100mL to handle subsequently solution, adopt the saturated sodium bicarbonate aqueous solution neutralization.Organic layer adopted dried over mgso and remove and desolvate by rotary evaporation.Be loaded into remaining resistates on the silicagel column and employing hexane wash-out.Output is 5.8g (45%).
Lithium 4-[3 ', 5 ' di-tert-butyl-phenyl]-2-sec.-propyl indenes
With 4-[3 ', 5 '-di-tert-butyl-phenyl]-(5.8g 17mmol) is dissolved in the 80mL pentane 2-sec.-propyl indenes.In this solution, add the n-BuLi (2.5M in hexane) of 6.6mL and allow reaction at room temperature to stir 4 hours.White solid precipitates from solution and this solid is filtered collection by frit and adopts other pentane washing.Output is 5.0g (87%).
The silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-sec.-propyl indenes
With 9, (1.1g 8.5mmol) is dissolved among the THF of 80mL 9-two chloro-9-silicon fluorenes.In this solution, slowly be incorporated as the lithium 4-[3 ' of dried powder, 5 '-di-tert-butyl-phenyl]-(3.0g's 2-sec.-propyl indenes 8.5mmol) and with solution stirring spends the night.After at this moment, in a vacuum except that desolvating and resistates being dissolved in ether.Solution is filtered to remove LiCl and to remove the crude product (3.9g) that desolvates and be used as next step in a vacuum by frit.
[9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-sec.-propyl indenes)] ZrCl
2
Will (3.9g 4.6mmol) dissolves in the 50mL ether from the thick solid of previous steps.Slowly adding n-BuLi (3.7mL, the 2.5M in hexane) in this solution also at room temperature stirred 3 hours.Solution is cooled to-30 ℃ and will be the ZrCl of dried powder
4(1.1g, 4.6mmol) adding was also at room temperature stirred 2 hours.Solvent is removed under vacuum and toluene is joined in the thick resistates.Solution filtered to remove LiCl filtrate is concentrated and under heating, heat pentane.Solution is cooled off with induced crystallization.The output of pure racemic isomer is 280mg (6.0%).
Loaded metal ocene catalyst system 4
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)
-2-sec.-propyl indenes)] close zirconium
In the 100mL round-bottomed flask, with the dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-sec.-propyl indenes)] close zirconium (0.090g) join MAO solution (6.74g, 7.2mL) in and stirred 20 minutes.This material is filtered and adopts toluene (14mL) washing by medium frit funnel.In bonded filtrate, add dehydrated silica (4.0g, Davison 948Regular, 600 ℃ of dehydrations).This slurry was stirred 20 minutes, then under 40 ℃ under vacuum on rotatory evaporator dry 2 minutes up to liquid evaporation with amount to about 2 hours 20 minutes with solid is further dry then.The catalyst recovery of load is a lavender, free-flowing solid (5.17g).
Embodiment 5
Dichloro [9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)
-2-sec.-propyl indenes)] close zirconium
2,2 '-'-dibromobiphenyl
(47.3g, 0.2mol) in the stirred solution, the n-BuLi that adds 76.4mL is (at Et to the adjacent dibromobenzene in the anhydrous THF of 450mL
21.0M among the O).The adjacent dibromobenzene solution of cooling in dry ice/acetone batch.Allow the yellow-green colour reaction mixture to be warming to 5 ℃ and then reaction mixture is adopted 5% hydrochloric acid hydrolysis of 100mL.Adopt 4 * 20mL part extracted with diethyl ether 4 times with the layer separation of acquisition and with water layer.The ether washes combined with original organic layer and pass through dried over sodium sulfate, filter, and reach 70 ℃ up to distillation temperature by distilling to concentrate.With resistates adopt the 50mL dehydrated alcohol handle and cooling with obtain 2,2 '-'-dibromobiphenyl.Output is 2.32g (7.4%).
9,9-two chloro-9-silicon fluorenes
(3.33g 0.08mol) adopts the pentane washing, carefully cuts into small pieces, and is suspended in the Et of 150mL with the lithium line
2Among the O.Stir simultaneously, in 1 hour, drip in the 100mL ether 2,2 '-'-dibromobiphenyl (25g, 0.08mol) and made contents stirred 10 hours.Mixture is filtered to remove any unreacted Li and LiBr by frit.Pack into filtrate in the feed hopper and slowly splash into the Et that is included in 200mL
2SiCl among the O
4(50g is in solution 0.08mol).After adding, content was at room temperature stirred 5 hours.Under vacuum, remove and desolvate and add the 30mL pentane.Solution is filtered to remove LiCl and to remove under vacuum once more and desolvate.Then solid is packed into sublimer and it is being distilled under the perfect vacuum under 150 ℃.Output is 10.0g (51%).
4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes
With 4-chloro-2-sec.-propyl indenes (10g, 54mmol) and NiCl
2(PPh
3)
2(1.8g 2.8mmol) is dissolved in the Et of 150mL
2Among the O.Under vigorous stirring, be incorporated as Et
23 of O solution, 5-3,5-dimethylphenyl magnesium bromide (54mmol) also at room temperature will react to stir and spend the night.After stirred overnight, will react and adopt H
2The slow quenching of O is with the unreacted Grignard reagent that neutralizes.Adopt the 10%HCl (aq) of 100mL to handle subsequently solution, adopt the saturated sodium bicarbonate aqueous solution neutralization.Organic layer adopted dried over mgso and remove and desolvate by rotary evaporation.Be loaded into remaining resistates on the silicagel column and employing hexane wash-out.Output is 5.5g (39%).
Lithium 4-[3 ', 5 '-3,5-dimethylphenyl]-2-sec.-propyl indenes
With 4-[3 ', 5 '-3,5-dimethylphenyl]-(5.6g 24mmol) is dissolved in the 80mL pentane 2-methyl indenes.In this solution, add the n-BuLi (2.5M in hexane) of 9.6mL and reaction was at room temperature stirred 4 hours.White solid precipitates from solution and this solid is filtered collection by frit and adopts other pentane washing.Output is 4.5g (80%).
9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes
With 9, (1.4g 11mmol) is dissolved among the THF of 80mL 9-two chloro-9-silicon fluorenes.In this solution, slowly be incorporated as the lithium 4-[3 ' of dried powder, 5 '-3,5-dimethylphenyl]-(3.0g's 2-methyl indenes 11mmol) and with solution stirring spends the night.After at this moment, in a vacuum except that desolvating and resistates being dissolved in ether.Solution is filtered to remove LiCl and to remove the crude product (2.1g) that desolvates and be used as next step in a vacuum by frit.
[9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes)] ZrCl
2
Will (2.1g 3.2mmol) dissolves in the 50mL ether from the thick solid of previous steps.Slowly adding n-BuLi (2.56mL, the 2.5M in hexane) in this solution also at room temperature stirred 3 hours.Solution is cooled to-30 ℃ and also will be the ZrCl of dried powder
4(0.74g 3.2mmol) adds and at room temperature stirred 2 hours.Solvent is removed under vacuum and toluene is joined in the thick resistates.Solution filtered to remove LiCl filtrate is concentrated and under heating, add pentane.Solution is cooled off with induced crystallization.The output of pure racemize/meso metallocenes is 120mg (3.8%).
Loaded metal ocene catalyst system 5
Dichloro racemize/meso [9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)
-2-sec.-propyl indenes)] close zirconium/MAO
In the 100mL round-bottomed flask, with dichloro racemize/meso [9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes)] close zirconium (0.076g) join MAO solution (6.74g, 7.2mL) in and stirred 20 minutes.This material is filtered and adopts toluene (14mL) washing by medium frit funnel.In bonded filtrate, add dehydrated silica (4.0g, Davison 948 Regular, 600 ℃ of dehydrations).This slurry was stirred 20 minutes, then under 40 ℃ under vacuum on rotatory evaporator in dry 2 minutes up to liquid evaporation with amount to about 2 hours 30 minutes with solid is further dry then.The catalyst recovery of load is a mulberry, free-flowing solid (5.06g).
Embodiment 6
Dimethyl rac-9-silicon fluorenes double-basis (2-methyl indenyl) is closed zirconium
9-silicon fluorenes, 9,9-pair-2-methyl indenes
(3.34g 24.52mmol) joins 9, and (3.08g is 12.26mmol) at Et for 9-two chloro-9-silicon fluorenes with solid 2-methyl indenyl lithium
2At room temperature stirred 2 hours in the stirred solution among the O (about 25mL) and with the mixture that obtains.Solvent is removed and residue extracted is gone into CH
2Cl
2In (about 75mL), filter and remove and desolvate, obtain white powder, this powder is adopted pentane (about 50mL) washing and dry under vacuum, stay 9-silicon fluorenes into white powder, 9,9-pair-2-methyl indenes (3.80g, 71%).
9-silicon fluorenes, 9, the preparation of 9-pair-2-methyl indenyl two lithiums
With 9-silicon fluorenes, 9,9-pair-(3.80g is 8.66mmol) at Et for 2-methyl indenes
2Slurry among the O (about 25mL) adopts n-Butyl Lithium (the 1.6M solution of 12mL in hexane) to handle and the mixture that obtains was at room temperature stirred 1 hour, produces light yellow precipitate.Mixture is filtered to separate faint yellow solid, this solid is dry under vacuum, obtain 9-silicon fluorenes, 9,9-pair-2-methyl indenyl two lithiums ● (Et
2O)
0.5(3.80g, 88%).
Dimethyl 9-silicon fluorenes, 9,9-is two-preparation that 2-methyl indenyl closes zirconium
With 9-silicon fluorenes, 9,9-pair-2-methyl indenyl two lithiums ● (Et
2O)
0.5(1.83g, 3.69mmol) and ZrCl
4(0.95g, 4.08mmol) mixture in benzene (about 25mL) at room temperature stirred 80 minutes, produced orange solids.Adopt hexane wash with the mixture filtration with orange solids.When mixing with benzene filtrate, hexane wash produces yellow solid and this mixture is filtered to remove yellow solid.Solvent is removed from the benzene-hexane filtrate that obtains, produced orange solids.With second kind of orange solids adopt the benzene washing once with adopt the pentane washed twice and dry under vacuum.The slurry of this orange solids in benzene (about 10mL) adopted CH
3(0.8mL is at Et for MgBr
23.0M solution among the O) handle and mixture was at room temperature stirred 15 minutes.(about 2-3mL) joins in the mixture Jiang diox, and filtering mixt is to produce glassy yellow filtrate.Solvent is removed from filtrate under vacuum, obtained pure dimethyl rac-9-silicon fluorenes, 9,9-pair-2-methyl indenyl closes zirconium (0.035g, 1.7%).
Polymerization
The isotactic polyprophlene homopolymer
It is as follows to adopt the load catalyst system of above-mentioned preparation (except that embodiment 6 described below) to produce the polymerization procedure of homopolymer.Adopting the cleaning of propylene steam washing, in two liters of autoclaves of exsiccant, add the TEAL scavenging agent (0.3mL, 1.5M).Add hydrogen as indication at this point.The quantity of hydrogen is the 1.55mmol that increases psi for each, as shown in Table.Reactor is closed and is adopted the filling of 800mL liquid propene.After reactor heating arrives the polymerization temperature of indication, add catalyzer by adopting propylene (200mL) washing.In the time of indication, typically after 1 hour,, and discharge excessive propene with reactor cooling.Polymkeric substance is removed and drying.
Use dimethyl rac-9-silicon fluorenes two (2-methyl indenyl) to close zirconium as catalyst precursor
Polymerization-isotactic polyprophlene homopolymer program
Under nitrogen purge, in two liters of autoclaves of dry cleansing, add the solution of triisobutyl aluminium (TIBAL) scavenging agent (0.3mL in toluene by volume 10% solution) in toluene (0.7mL).Autoclave is adopted the filling of 300mL liquid propene and is heated to 60 ℃.By in toluene (about 1-1.5mL),, adopt the 100mL propylene to wash this catalyzer into autoclave with equimolar amount catalysts precursor and trityl tetrafluoro phenyl boronate 5 minutes time of activator formation catalyzer.Polymerization was carried out 15 minutes, thereafter with reactor cooling and discharge excessive propene.Polymkeric substance is removed and drying.
Random copolymers (RCP)
It is as follows to adopt the load catalyst system of above-mentioned preparation to produce the polymerization procedure of random copolymers.Adopting the cleaning of propylene steam washing, in two liters of autoclaves of exsiccant, add the TEAL scavenging agent (0.3mL, 1.5M).Add hydrogen as indication at this point.The quantity of hydrogen is the 1.55mmol that increases psi for each, as shown in Table.Reactor is closed and is adopted the filling of 800mL liquid propene.After reactor heating to 60 ℃, add ethylene partial pressure and then by adopting propylene (200mL) washing to add catalyzer as indication.Add ethylene gas to keep constant compression force.In the time of indication, typically after 1 hour, with reactor cooling and discharge excessive propene and ethene.Polymkeric substance is removed and drying.
Impact-resistant copolymerized thing (ICP)
It is as follows to adopt the load catalyst system of above-mentioned preparation to produce the polymerization procedure of ICP.Adopting the cleaning of propylene steam washing, in two liters of autoclaves of exsiccant, add the TEAL scavenging agent (0.3mL, 1.5M).Add hydrogen at this point.The quantity of hydrogen is the 1.55mmol that increases psi for each, as shown in Table.Reactor is closed and is adopted the filling of 800mL liquid propene.After reactor heating to 70 ℃, add catalyzer by adopting propylene (200mL) washing.In the time of indication, typically after 1 hour, reactor is vented to about 170psig pressure and then under the speed of indicating, the ethylene/propene gaseous mixture is kept 200psig simultaneously by reactor.When the gas phase stage finishes, typically 90-150 minute, with the reactor exhaust with at N
2Following cooling.Granular ICP polymkeric substance is removed and drying.
The contrast metallocene catalyst system 1 of working load carries out aggregation test 1-14.The results are shown in Table 1 and 2.
The contrast metallocene catalyst system 2 of working load carries out aggregation test 15-25.The results are shown in Table 3 and 4.
The metallocene catalyst system 3 of working load carries out aggregation test 65-71.The results are shown in Table 5 and 6.
The metallocene catalyst system 4 of working load carries out aggregation test 72-88.The results are shown in Table 7 and 8.
The metallocene catalyst system 5 of working load carries out aggregation test numbers 133 and 134.The results are shown in Table 9 and 10.
The metallocene catalyst system 6 of working load carries out aggregation test numbers 135 and 136.The results are shown in Table 11.
Polymer analysis
(GPC) carries out molecular weight measurement according to following technology by gel permeation chromatography.Use is equipped with Shodex (Showa Denko) AT-806MS post and differential refractive index (DRI) detector, at 145 ℃ of Waters 150C gel permeation chromatographies of operating down, adopt 1,2, the 4-trichlorobenzene is measured molecular weight and molecular weight distribution as moving phase under the 1.0mL/min flow.It is 300 microlitres that sample injects volume.Use narrow polystyrene standards Calibration Column to produce the general calibration curve.Use k=8.33 * 10
-5Set up the polypropylene calibration curve with a=0.800 as the Mark-Houwink coefficient.The Waters that use moves on the VAX6410 computer " Expert-Ease " software carries out numerical analysis.
Use the calibration of forming the sample acquisition of determining by NMR from it by FT-IR, measure the ethene quantity in the random copolymers.
The DSC fusing point measures and is reported to second fusing point on commercial DSC instrument.With weight less than 10 milligrams polymer particles material be heated to 230.0 ℃ following 10 minutes and under 10 ℃/minute, be cooled to 50 ℃ then from 230 ℃.With sample remain on 50 ℃ following 5 minutes.Then when under 10 ℃/minute sample being write down fusion for the second time when 50 ℃ are heated to 200 ℃.Peak temperature is recorded as second fusing point.
ICP polymkeric substance extracting process
The ICP polymkeric substance is dissolved in hot diformazan benzo makes its cool overnight then.After filtering, with the insolubles drying.Xylene soluble partly evaporated and reclaim dissolved material.In naphthalane, pass through to use currently known methods and instrument such as Schott A VSPro viscosity self-actuated sampler to measure the IV that reclaims dissolved material down at 135 ℃.
Under very high ICP MFR, this method can extract some lower molecular weight isotaxy PP and therefore reduce the IV that absorbs.
ICP polymkeric substance stage division
The ICP sample is delivered to Polyhedron Laboratories, and Inc is by GPC classification and analysis.The general description of the program document J.C.Randall that sees reference, J.Poly.Sci.: part A polymer chemistry, 36 volumes, 1527-1542 (1998).
Table 1
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl)
2Close zirconium/MAO-simultaneous test # metalloscene catalyst body temperature degree (℃) catalyst amounts output (g) efficient C2=H2 splitting time C
2 =/ C
3 =Flow
System's (contrast) is (min) (1/min) 11 60 67 274.7 4.10 00 60-2 1 60 45 71.7 1.59 00 60-3 1 60 40 134.1 3.35 10 0 60-4 1 60 42 221.5 5.27 20 0 60-5 1 60 30 121.3 4.04 55 0 60-6 1 60 30 130.2 4.34 70 0 60-7 1 60 30 101.8 3.39 20 0 60-8 1 70 45 293.5 6.52-50 60-9 1 70 31 198.9 6.42-50 60-.10 1 70 30 291.9 9.73-50 60/150 4.0/1.011 1 70 30 231.3 7.71-50 60/90 4.0/1.012 1 70 30 224.8 7.49-50 60/90 4.1/0.913 1 70 30 209.9 7.00-50 60/90 3.6/1.414 1 70 30 208.2 6.94-50 60/90 4.0/1.0 of (Kg/g cat) (δ psi) (δ psi) (mg)
Table 2
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-phenyl indenyl)
2Close the final fusing point of total rubber in zirconium/total ethylene rubber of MAO-simultaneous test # metalloscene catalyst (℃) MW MWD multipolymer
( ) ( wt％ ) ( wt％ ) ( wt％ ) MFR ( g/10min ) IV1 1---0.16 149.2 600.0 2.002 1---0.54 148.2 664.9 1.923 1 0.67--0.84 142.0 349.0 2.094 1 1.28--2.57 138.4 280.0 1.955 1 3.77--6.48 121.4 255.0 2.046 1 4.43--5.95 116.0 301.0 2.307 1 1.44--2.05 137.5 330.4 2.238 1---99.6 150.3 120.6 3.019 1---58.95 150.9 135.7 3.1510 1 13.23 49.20 26.89 178.5 151.2 81.2 3.37 0.752011 1 7.58 47.37 16.00 134.05 150.6 98.4 3.25 0.68712 1 7.82 50.04 15.63 127.16 150.0 100.4 3.11 0.70813 1 5.3 38.96 13.60 201.9 150.43 91.2 3.28 0.77914 1 0.47 64.32 0.73 97.1 150.8 116.8 3.42
Table 3
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-[1-naphthyl] indenyl)
2Close zirconium/MAO-simultaneous test # metalloscene catalyst catalyst amounts output (g) efficient C2=H2 splitting time C
2 =/ C
3 =Flow
System (contrast) is (min.) (1/min) 15 2 76 332.0 4.37-40 60-16 2 61 260.8 4.28-35 60/120 4.0/1.017 2 60 266.2 4.44-35 60/120 4.4/0.618 2 60 272.6 4.54-35 60/120 4.2/0.819 2 61 196.9 3.23-35 60-20 2 61 121.2 1.99 20 5 60-21 2 61 118.1 1.94 30 5 60-22 2 61 137.7 2.26 40 5 60-23 2 62 141.9 2.29 50 5 60-24 2 60 138.6 2.31 40 10 60-25 2 62 234.8 3.79-50 60/90 4.0/1.0 of (Kg/g cat) (δ psi) (δ psi) (mg)
Table 4
Dichloro racemize dimethyl-silicon two bases (2-methyl-4-[1-naphthyl] indenyl)
2Close zirconium/MAO-simultaneous test # metallocenes and urge the IV of the final fusing point MW of the second total rubber MWD multipolymer in total ethylene rubber
MFR
Change agent system (wt%) alkene (wt%) (wt%) (g/10min) (℃)
(contrast) 15 2---4.08 150.5 299.1 2.78-16 2 7.76 47.27 16.42 4.76 151.7 212.1 2.68 1.656717 2 16.39 61.45 26.67 1.3 150.8 230.9 3.33 1.704818 2 9.74 51.52 18.91 4.98 151.0 210.4 2.96 1.712719 2---3.12 151.0 278.0 2.49-20 2 1.27--0.19 138.43 603.0 2.59-21 2 1.75--0.15 136.10 614.8 2.59-22 2 2.25--0.196 131.90 604.5 2.31-23 2 2.82--0.213 127.83 579.0 2.36-24 2 2.39--0.225 131.63 542.8 2.41-25 2 3.803 48.39 7.86 4.95 151.43 176.8 2.94 1.425
Table 5
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-methyl indenyl)] close zirconium/MAO test # metallocenes urge the catalyst amounts temperature (℃) yield efficiency H2 splitting time C
2 =/ C
3 =Flow (1/min)
Change agent system (g) (Kg/g cat) (δ psi)
(mg) (min.)65 3 299 60 13.2 0.04 0 6 -66 3 61 60 35.0 0.57 0 60 -67 3 60 70 81.3 1.4 35 60 -68 3 32 70 96.2 3.0 35 60/90 4.0/1.069 3 30 70 93.3 3.1 35 60/120 4.0/1.070 3 31 70 83.9 2.7 35 60/90 3.6/1.471 3 30 70 77.8 2.6 35 60/120 4.2/0.8
Table 6
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-methyl indenyl)] close the final MFR fusing point of second total rubber in zirconium/total ethylene rubber of MAO test # metallocene catalyst (℃) IV of MW MWD multipolymer
Agent system (wt%) alkene (wt%) is (g/10min) 65 3---0.65 156.17 412 149.3-66 3---0.075 156.23 710.8 2.71-67 3---3.59 156.5 270.7 2.82-68 3 4.814 54.74 8.8 69.59 155.43 119.4 3.22 0.7069 3 6.624 49.55 13.4 9.84 156.5 200.0 3.56 0.7770 3 3.095 42.72 7.2 14.54 155.97 194.5 3.52 0.7471 3 7.691 54.36 14.1 10.61 157.17 207.1 3.50 1.30 (wt%)
Table 7
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-sec.-propyl indenyl)] close zirconium/MAO test # metallocene catalyst catalyst amounts temperature (℃) output (g) efficient C2=H2 splitting time C
2 =/ C
3 =Flow
( mg ) ( Kg/g cat ) ( δpsi ) ( δpsi ) ( min. ) ( 1/min ) 72 4 300 60 11.8 0.04-0 10-73 4 120 70 116.8 0.97-10 60-74 4 121 70 127.6 1.1-10 60/90 4.0/1.075 4 62 70 126.4 2.0-20 60-76 4 63 70 139.5 2.2-35 60-77 4 60 70 151.4 0.40-20 60/90 4.2/0.878 4 62 70 246.2 4.0-35 60/90 4.2/0.879 4 60 70 218.9 3.6-35 60/120 4.2/0.880 4 62 70 249.8 4.0-50 60-81 4 61 70 233.1 3.8-35 60/120 4.4/0.682 4 61 60 184.2 3.0 10 20 60-83 4 60 60 202.6 3.4 20 20 60-84 4 60 60 209.6 3.5 30 20 60-85 4 60 70 157.9 2.6-35 30/120 4.4/0.686 4 63 70 200.5 3.2-35 60-87 4 60 70 223.9 3.7-35 60/120 4.2/0.888 4 60 70 196.1 3.3-35 60/180 4.2/0.8
Table 8
The dichloro racemize [9-silicon fluorenes two (4-(3 ', 5 '-di-tert-butyl-phenyl)-2-sec.-propyl indenyl)] close the final fusing point of second total rubber (wt%) in zirconium/MAO test total ethene of # metallocene catalyst (wt%) rubber (℃) IV of MW MWD multipolymer
( wt％ ) MFR ( g/10min ) 72 4---0.82 160.78 381.6 2.01-73 4---2.85 159.17 267.3 1.80-74 4 4.297 32.93 13.0 3.56 161.1 255.7 2.03 2.9275 4---11.53 158.83 191.5 2.25-76 4---24.03 159.43 166.6 1.98-77 4 2.449 32.63 7.5 12.0 159.7 194.7 2.11 2.0678 4 2.012 42.53 4.7 110.44 159.1 116.8 2.48 2.2179 4 3.389 40.38 8.4 32.37 158.5 173.2 2.71 2.5580 4---499.99 157.9 85.7 2.25-81 4 4.093 47.35 8.6 41.24 158.57 147.0 2.32 2.8782 4 0.87--9.54 151.17 204.2 2.39-83 4 1.4--18.53 146.17 182.3 2.14-84 4 2.4--24.5 138.5 172.2 1.93-85 4 4.732 46.4 10.2 118.7 158.23 119.7 2.39 86 4---28.17 158.37-87 4 3.081 44.21 7.0 61.24 158.8388 4---15.7 158.77-
Table 9
Dichloro [9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes)] close zirconium/MAO test # metallocenes urge temperature (℃) catalyst amounts yield efficiency H2 (δ psi) time (min.)
Change agent system (g) (Kg/g cat)
(mg)133 5 60 302 6.0 0.02 0 60134 5 70 121 18.4 0.15 10 60
Table 10
Dichloro [9-silicon fluorenes two (4-(3 ', 5 '-3,5-dimethylphenyl)-2-sec.-propyl indenes)] close zirconium/MAO test # metallocenes urge final MFR fusing point (℃) MW MWD
Change agent system (g/10 min.) 133 5-150.9,467.6 4.98
minor?156.52134 5 32.07 156.5 104.8 2.71
Table 11
Use dimethyl rac-9-silicon fluorenes two, (2-methyl indenyl) closes the aggregation test # T of zirconium, (℃) catalyst precursor, (mg) activator, (mg) output, (g) fusing point, (℃) MW MWD135 60 1.20 1.98 49.3 148.7 72,610 1.93136 60 0.90 1.50 50.4 149.8 72,215 1.97
Although by describing and illustrated the present invention with reference to specific embodiment, what can be appreciated by those skilled in the art is to the invention provides it and self do not change in many differences of this explanation.Then, only should be used for determining the purpose of true scope of the present invention with reference to appended claim owing to these reasons.
Claims (23)
- Two (indenyl) Metallocenic compounds of a bridge joint wherein the bridge joint between indenyl 1-position be the group of following general formula:
R wherein 17-R 24Can be identical or different, and each is hydrogen atom, C 1-C 10Alkyl, C 1-C 10Alkoxyl group, C 6-C 10Aryl, C 6-C 10Aryloxy, C 2-C 10Thiazolinyl, C 2-C 4Thiazolinyl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 8-C 40Arylalkenyl, OH group or halogen atom, or two or more adjacent R 17-R 24, comprise R 20And R 21, form one or more and phenyl condensed ring with the atom between two parties of phenyl; WithM 2Be carbon, silicon, germanium or tin,Optionally on the rest position of indenyl rings, replace. - 2. compound of representing by following general formula:
Wherein M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;R 1And R 2Can be identical or different, and each is hydrogen atom, C 1-C 10Alkyl, C 1-C 10Alkoxyl group, C 6-C 10Aryl, C 6-C 10Aryloxy, C 2-C 10Thiazolinyl, C 2-C 4Thiazolinyl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 8-C 40Arylalkenyl, OH group or halogen atom; Or R 1And R 2Be conjugated diene, it is optionally replaced by one or more alkyl, three (alkyl) silyl or three (alkyl) silyl alkyl, and this diolefine contains 30 atoms that are not counted in hydrogen at the most;R 3And R 4Can be identical or different, and each be hydrogen atom, halogen atom, can halogenated C 1-C 10Alkyl, can halogenated C 6-C 10Aryl, C 2-C 10Thiazolinyl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 8-C 40Arylalkenyl ,-NR ' 2,-SR ' ,-OR ' ,-OSiR ' 3Or-PR ' 2Group, wherein: R ' is halogen atom, C 1-C 10Alkyl, C 6-C 10One of aryl;R 13Be
Wherein: R 17-R 24, and M 2Such as claim 1 definition; WithRadicals R can be identical or different and each have for R 3And R 4Described implication, or two adjacent R groups are combined together to form ring with the atom that is connected them. - 3. the compound of claim 1 or claim 2, wherein M 2Be silicon.
- 4. the compound of claim 2 or claim 3, wherein M is zirconium, titanium or hafnium.
- 5. the compound of claim 4, wherein M is a zirconium.
- 6. each compound, wherein R among the claim 2-4 4Not hydrogen.
- Among the claim 1-5 each and the compound represented by following general formula:
R 5-R 7Can be identical or different and each be hydrogen atom or as for R 3Group or two or more adjacent radicals R of definition 5-R 7Form one or more rings with the atom that connects them;WithR 8, R 9, R 10, R 11And R 12Can be identical or different and each have described implication for R. - 8. the compound of claim 7, wherein R 3Be identical C 1-C 4Alkyl.
- 9. the compound of claim 8, wherein R 3Both are methyl.
- 10. the compound of claim 7, wherein:Identical and each be C 1-C 10Alkyl; WithM 2Be silicon.
- 11. each compound, wherein R among the claim 7-10 4-R 7It is hydrogen atom.
- 12. each compound, wherein R among the claim 1-11 17-R 24Be hydrogen.
- 13. each compound, wherein R among the claim 7-12 9And R 11Identical or different and each be the IVA family group that contains 2-20 carbon atom.
- 14. the compound of claim 13, wherein R 9And R 11Identical or different and each be butyl, aryl, sec.-propyl or fluoroalkyl.
- 15. the compound of claim 14, wherein R 9And R 11Each is the tertiary butyl.
- 16. a catalyst composition comprises each compound and the reaction product of promotor among the claim 1-15.
- 17. a load catalyst system comprises solid support material, the product of each compound among one or more promotors and one or more claims 1-15.
- 18. the catalyst system of claim 17, wherein solid support material comprises magnesium chloride, silicon-dioxide or its binding substances.
- 19. each catalyst composition among the claim 16-18, wherein promotor comprises one or more non-coordination anion activators.
- 20. each catalyst composition among the claim 16-18, wherein promotor comprises one or more alkylaluminoxane activators.
- 21. the catalyst composition of claim 19, wherein promotor comprises non-coordination anion activator and alkylaluminoxane activator.
- 22. a polymerization process is included under the suitable polymerizing condition among one or more monomers of contact and the claim 16-21 each catalyst composition.
- 23. the method for claim 22, wherein monomer is selected from ethene, propylene, 1-butylene and 1-hexene.
Applications Claiming Priority (28)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21545900P | 2000-06-30 | 2000-06-30 | |
| US21559700P | 2000-06-30 | 2000-06-30 | |
| US60/215,597 | 2000-06-30 | ||
| US60/215,459 | 2000-06-30 | ||
| US09/619,759 US6376408B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/619,757 | 2000-07-19 | ||
| US09/619,751 | 2000-07-19 | ||
| US09/620,302 US6376411B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,359 | 2000-07-19 | ||
| US09/619,764 | 2000-07-19 | ||
| US09/619,748 US6376627B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,175 US6376410B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,522 US6380124B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,304 US6376412B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,303 US6414095B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,341 | 2000-07-19 | ||
| US09/619,750 | 2000-07-19 | ||
| US09/620,302 | 2000-07-19 | ||
| US09/619,764 US6376409B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,046 | 2000-07-19 | ||
| US09/620,198 US6380330B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/619,749 US6376407B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/619,752 US6399723B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/620,198 | 2000-07-19 | ||
| US09/619,750 US6380120B1 (en) | 2000-06-30 | 2000-07-19 | Metallocene compositions |
| US09/619,749 | 2000-07-19 | ||
| US09/620,613 | 2000-07-19 | ||
| US09/620,303 | 2000-07-19 |
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| CN1274701C CN1274701C (en) | 2006-09-13 |
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| CNB018133959A Expired - Fee Related CN1274701C (en) | 2000-06-30 | 2001-05-21 | Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization |
| CNB018134017A Expired - Lifetime CN1332966C (en) | 2000-06-30 | 2001-05-21 | Bridged bis (indenyl) metallocene compounds |
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| CNB018134017A Expired - Lifetime CN1332966C (en) | 2000-06-30 | 2001-05-21 | Bridged bis (indenyl) metallocene compounds |
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| EP (2) | EP1313746B1 (en) |
| JP (1) | JP2004502699A (en) |
| CN (2) | CN1274701C (en) |
| AT (1) | ATE300550T1 (en) |
| DE (1) | DE60112307T8 (en) |
| WO (1) | WO2002002576A1 (en) |
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| EP4257640A1 (en) | 2022-04-04 | 2023-10-11 | Borealis AG | Pipe comprising a polypropylene composition |
| WO2023208875A1 (en) | 2022-04-26 | 2023-11-02 | Borealis Ag | A process for recycling polypropylene films |
| WO2023208984A1 (en) | 2022-04-28 | 2023-11-02 | Borealis Ag | Process for producing random propylene copolymers comprising c4-c12-alpha olefin comonomer units |
| EP4286476A1 (en) | 2022-05-31 | 2023-12-06 | Borealis AG | Glass fiber composite |
| WO2024013128A1 (en) | 2022-07-11 | 2024-01-18 | Borealis Ag | A propylene-ethylene random copolymer for pipe applications |
| WO2024013126A1 (en) | 2022-07-11 | 2024-01-18 | Borealis Ag | A process for preparing propylene-ethylene random copolymers for pipe applications |
| WO2024042070A1 (en) | 2022-08-23 | 2024-02-29 | Borealis Ag | Alpha-nucleated propylene/ethylene/1-butene terpolymer compositions for blown and cast films |
| WO2024061958A1 (en) | 2022-09-21 | 2024-03-28 | Borealis Ag | Propylene/ethylene/1-butene terpolymer compositions with multimodal base polymer |
| WO2024094663A1 (en) | 2022-10-31 | 2024-05-10 | Borealis Ag | Process for producing high-flow heterophasic propylene copolymer compositions |
| WO2024094676A1 (en) | 2022-10-31 | 2024-05-10 | Borealis Ag | Compositon for automotive exterior parts |
| EP4389776A1 (en) | 2022-12-20 | 2024-06-26 | Borealis AG | Process |
| EP4389783A1 (en) | 2022-12-20 | 2024-06-26 | Borealis AG | Catalyst transition process |
| WO2024133044A1 (en) | 2022-12-23 | 2024-06-27 | Borealis Ag | Process for producing a polypropylene homo- or copolymer |
| WO2024133046A1 (en) | 2022-12-23 | 2024-06-27 | Borealis Ag | Process for producing a polypropylene copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0629632B2 (en) * | 1993-06-07 | 2015-01-21 | Mitsui Chemicals, Inc. | Polypropylene |
| DE19544828A1 (en) * | 1995-12-01 | 1997-06-05 | Hoechst Ag | High molecular copolymers |
| CA2262493A1 (en) * | 1997-03-07 | 1998-09-17 | Targor Gmbh | Method for producing olefin polymers with a higher melting point |
| US6160072A (en) * | 1997-05-02 | 2000-12-12 | Ewen; John A. | Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes |
| EP1031582A1 (en) * | 1999-02-26 | 2000-08-30 | Fina Research S.A. | Use and production of polypropylene |
-
2001
- 2001-05-21 DE DE60112307T patent/DE60112307T8/en active Active
- 2001-05-21 JP JP2002507828A patent/JP2004502699A/en active Pending
- 2001-05-21 WO PCT/US2001/016573 patent/WO2002002576A1/en active IP Right Grant
- 2001-05-21 CN CNB018133959A patent/CN1274701C/en not_active Expired - Fee Related
- 2001-05-21 EP EP01941551A patent/EP1313746B1/en not_active Expired - Lifetime
- 2001-05-21 EP EP05010280A patent/EP1632506A1/en not_active Withdrawn
- 2001-05-21 AT AT01941551T patent/ATE300550T1/en not_active IP Right Cessation
- 2001-05-21 CN CNB018134017A patent/CN1332966C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107847920A (en) * | 2015-07-15 | 2018-03-27 | 埃克森美孚化学专利公司 | Substituted double indenyl metallocene catalyst compounds comprising Si Si abutments |
| CN114127130A (en) * | 2019-05-29 | 2022-03-01 | 博里利斯股份公司 | Improved preparation of catalyst systems |
| CN114829419A (en) * | 2019-12-17 | 2022-07-29 | 米其林集团总公司 | Catalytic system based on metallocenes and diorganomagnesium |
| CN114829419B (en) * | 2019-12-17 | 2023-12-12 | 米其林集团总公司 | Catalytic system based on metallocenes and diorganomagnesium |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE300550T1 (en) | 2005-08-15 |
| WO2002002576A1 (en) | 2002-01-10 |
| CN1274701C (en) | 2006-09-13 |
| DE60112307T2 (en) | 2006-05-24 |
| CN1332966C (en) | 2007-08-22 |
| CN1444594A (en) | 2003-09-24 |
| EP1632506A1 (en) | 2006-03-08 |
| DE60112307D1 (en) | 2005-09-01 |
| EP1313746B1 (en) | 2005-07-27 |
| EP1313746A1 (en) | 2003-05-28 |
| JP2004502699A (en) | 2004-01-29 |
| DE60112307T8 (en) | 2007-02-15 |
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